EP2471897B1 - Method for reducing chloropropanols and formative substance thereof, glycidol fatty acid esters, in glyceride oils - Google Patents

Method for reducing chloropropanols and formative substance thereof, glycidol fatty acid esters, in glyceride oils Download PDF

Info

Publication number
EP2471897B1
EP2471897B1 EP10820654.1A EP10820654A EP2471897B1 EP 2471897 B1 EP2471897 B1 EP 2471897B1 EP 10820654 A EP10820654 A EP 10820654A EP 2471897 B1 EP2471897 B1 EP 2471897B1
Authority
EP
European Patent Office
Prior art keywords
oil
fatty acid
activated carbon
acid ester
chloropropanols
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP10820654.1A
Other languages
German (de)
French (fr)
Other versions
EP2471897A1 (en
EP2471897A4 (en
Inventor
Yoko Kurosawa
Hitomi Omori
Masamitsu Kuriyama
Akira Morita
Tomomi Inoue
Futoshi Yokomizo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuji Oil Co Ltd
Original Assignee
Fuji Oil Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=43826351&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2471897(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Fuji Oil Co Ltd filed Critical Fuji Oil Co Ltd
Publication of EP2471897A1 publication Critical patent/EP2471897A1/en
Publication of EP2471897A4 publication Critical patent/EP2471897A4/en
Application granted granted Critical
Publication of EP2471897B1 publication Critical patent/EP2471897B1/en
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/10—Refining fats or fatty oils by adsorption
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
    • A23D9/02—Other edible oils or fats, e.g. shortenings, cooking oils characterised by the production or working-up
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/04—Refining fats or fatty oils by chemical reaction with acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/12—Refining fats or fatty oils by distillation
    • C11B3/14—Refining fats or fatty oils by distillation with the use of indifferent gases or vapours, e.g. steam

Definitions

  • the present invention relates to a method for reducing chloropropanols and a formative substance thereof, glycidol fatty acid ester, in a glyceride fat or oil.
  • chloropropanol is a generic name of substances in which chlorine is bound to propanol, and it has previously been known that 3-chloropropanediol which is one of them is produced as a byproduct in a small amount mainly when an amino acid liquid such as soy sauce is produced. It is also said that 3-chloropropanediol is produced due to existence of fats and sodium chloride in a process of cooking foods.
  • Non-Patent Documents 1 and 2 Recently, it has been revealed that 3-chloropropanediol and glycidol are present as an ester in which they are bound to a fatty acid in edible fats and oils.
  • Glycidol is a compound in which 1- and 2-positions of glycerol are dehydration-condensed to form an epoxide.
  • Non-Patent Document 3 a glycidol fatty acid ester is present as a formative substance thereof.
  • Non-Patent Document 4 Moreover, several potential ways to reduce 3-MCPD esters in vegetable oils were discussed in Non-Patent Document 4. It concludes that 3-MCPD ester are formed mainly at the deodorization stage; the higher the deodorization temperature the higher the levels. Crude oil characteristics, e.g. diglyceride or chloride content are also an important factor, although there is no simple relationship. It further reports a number of trials that were done to reduce the 3-MCPD esters and mentions that no effect was found by treatment with active carbon (Non-Patent Document 4).
  • An object of the present invention is to provide a method for reducing chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester in a glyceride fat or oil.
  • the present inventors have intensively studied. As a result, they have found that chloropropanols and a glycidol fatty acid ester in a glyceride fat or oil can be reduced by treating a glyceride fat or oil after a bleaching and deodorization step with silica gel and/or basic activated carbon wherein the pH of the basic activated carbon is 9 or higher.
  • the present invention has been completed on the basis of these findings.
  • the present invention provides:
  • chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester in a glyceride fat or oil can be reduced.
  • the present invention can also be applied to edible refined fats and oils such as soybean oil, rapeseed oil, safflower oil, corn oil, sunflower oil, cottonseed oil, rice oil, olive oil, palm oil, coconut oil, palm kernel oil, sesame oil, beef tallow, lard, and fish oil which are subjected to a refining step such as bleaching and deodorization, and can be preferably applied to a palm-base fat or oil among them.
  • edible refined fats and oils such as soybean oil, rapeseed oil, safflower oil, corn oil, sunflower oil, cottonseed oil, rice oil, olive oil, palm oil, coconut oil, palm kernel oil, sesame oil, beef tallow, lard, and fish oil which are subjected to a refining step such as bleaching and deodorization, and can be preferably applied to a palm-base fat or oil among them.
  • the method of the present invention allows to reduce chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester in a glyceride fat or oil, by treating a glyceride fat or oil after a bleaching and deodorization step with silica gel and/or basic activated carbon.
  • the basic activated carbon is hydrophobic activated carbon which has been activated at a high temperature of 500°C or higher.
  • the pH of basic activated carbon is 9 or higher, preferably 10 or higher.
  • the effect of reducing chloropropanols and a glycidol fatty acid ester thereof in a glyceride fat or oil is higher.
  • the pH of activated carbon can be measured by the method described in JIS K 1474 "Activated Carbon Test Method".
  • Examples of a method of silica gel treatment and/or active carbon treatment in the present invention include a method of adding 0.1 to 5% by weight of silica gel and/or active carbon to a glyceride fat or oil, and mixing and contacting for a certain period under warming at 50 to 150°C and reduced pressure.
  • the glyceride fat or oil obtained by the method of the present invention has been reduced in the content of chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester.
  • chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester.
  • the content of chloropropanols and a glycidol fatty acid ester is measured by the following method by referring to the following reference. (Determination of total 3-chloropropane-1,2-diol (3-MCPD) in edible oils by cleavage of MCPD esters with sodium methoxide. Eur. J. Lipid Sci. Technol. 2008, 110, : 183-186 )
  • a fat or oil is dissolved in 1 ml of t-butyl methyl ether, 250 ⁇ l of a 20 ⁇ g/ml internal standard substance (3-MCPD-d 5 ethyl acetate solution) is added, and the mixture is mixed with 1 ml of a NaOCH 3 solution (0.5 mol/l NaOCH 3 in MeOH) and allowed to stand at room temperature for 10 minutes.
  • a NaOCH 3 solution 0.5 mol/l NaOCH 3 in MeOH
  • quantitation is carried out by using a molecular ion peak m/z 196 (3-MCPD) and m/z 201 (3-MCPD-d 5 ).
  • the above-mentioned method is adopted as a method of measuring 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester in Germany (Deutsche Deutschen fur Fettsch: DGF).
  • 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester in a glyceride fat or oil are hydrolyzed, and all of 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester that are present in a glyceride fat or oil are measured as 3-MCPD.
  • 3-MCPD 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester that are present in a glyceride fat or oil are measured as 3-MCPD.
  • 3-MCPD esters forming compounds is glycidol (oxirane-2-methanol)." (Ester-bound 3-chloropropane-1,2-diol (3-MCPD esters) and 3-MCPD forming substances: DGF Standard Methods Section C-Fats/C-III 18(09)).
  • the glyceride fat or oil obtained by the method of the present invention has been reduced in the content of a glycidol fatty acid ester.
  • the content of a glycidol fatty acid ester is measured by the following method.
  • quantitation is carried out in a positive ion mode using a precursor ion m/z 358, a product ion m/z 341 (glycidol stearic acid ester), a precursor ion m/z 356, a product ion m/z 339 (glycidol oleic acid ester), a precursor ion m/z 330, and a product ion m/z 313 (glycidol palmitic acid ester).
  • the detection limit is 0.5 ppm.
  • % means a weight basis.
  • the content of chloropropanols and a formative substance thereof in the resulting refined palm oil was 6.5 ppm.
  • the content of chloropropanols and a formative substance thereof in the refined palm oil after the adsorbent treatment was 4.8 ppm.
  • the content of chloropropanols and a formative substance thereof in the refined palm oil after the activated carbon treatment was 4.7 ppm.
  • the content of chloropropanols and a formative substance thereof in the refined palm oil after the activated carbon treatment was 4.5 ppm.
  • the content of chloropropanols and a formative substance thereof in the refined palm oil after the activated carbon treatment was 7.4 ppm.

Description

    Technical Field
  • The present invention relates to a method for reducing chloropropanols and a formative substance thereof, glycidol fatty acid ester, in a glyceride fat or oil.
    • Background Art
  • The "chloropropanol" is a generic name of substances in which chlorine is bound to propanol, and it has previously been known that 3-chloropropanediol which is one of them is produced as a byproduct in a small amount mainly when an amino acid liquid such as soy sauce is produced. It is also said that 3-chloropropanediol is produced due to existence of fats and sodium chloride in a process of cooking foods.
  • Recently, it has been revealed that 3-chloropropanediol and glycidol are present as an ester in which they are bound to a fatty acid in edible fats and oils (Non-Patent Documents 1 and 2).
  • Glycidol is a compound in which 1- and 2-positions of glycerol are dehydration-condensed to form an epoxide.
  • Further, recently, it has also been reported that, in a process of producing chloropropanols in a glyceride fat or oil, a glycidol fatty acid ester is present as a formative substance thereof (Non-Patent Document 3).
  • Moreover, several potential ways to reduce 3-MCPD esters in vegetable oils were discussed in Non-Patent Document 4. It concludes that 3-MCPD ester are formed mainly at the deodorization stage; the higher the deodorization temperature the higher the levels. Crude oil characteristics, e.g. diglyceride or chloride content are also an important factor, although there is no simple relationship. It further reports a number of trials that were done to reduce the 3-MCPD esters and mentions that no effect was found by treatment with active carbon (Non-Patent Document 4).
  • Regarding 3-chloropronediol fatty acid ester, there is no regulation such as an acceptable ingestion amount. In Europe, however, there is a tendency to evaluate on the assumption that fatty acids binding to 3-chloropropanediol fatty acid ester are entirely freed to turn into 3-chloropropanediol. Therefore, it is desirable to develop a technique for reducing the content thereof in a glyceride fat or oil.
  • In addition, also regarding a glycidol fatty acid ester, there is no toxicological data. However, it is desirable to develop a technique for reducing the content thereof in a glyceride fat or oil, as is the case with chloropropanols.
    • Prior Art Documents Non-Patent Documents
    • Non-Patent Document 1: Zelinková Z, Svejkovská B, Velí
      Figure imgb0001
      ek J, Dole
      Figure imgb0002
      al M.: Fatty acid esters of 3-chloropropane-1,2-diol in edible oils. Food Addit Contam. 2006 Dec; 23 (12): 1290-1298
    • Non-Patent Document 2: Erste Einschätzung zur Berwertung der in raffinierten pflnzlichen Fetten nach gewiesenen Gehalte von Glycidol-Fettsäureestern (Stellungnahme Nr. 007/2009 des BfR vom 10. März 2009)
    • Non-Patent Document 3: Dr. Rüdiger Weisshaar/Fatty acid esters of 3-MCPD: Overview of occurrence in different types of foods (ILSI Europe Workshop in association with the European Commission: 5-6 February 2009 Brussels, Belgium) (http://europe.ilsi.org/NR/rdonlyres/A1D194E7-BFA2-4A23-A673-15F1905300D5/0/Speaker6Weisshaar.pdf).
    • Non-Patent Document 4: Gerrit Van Duijn/Potential ways of reduction of 3-MCPD esters in vegetable oils (ILSI Europe Workshop on 3-MCPD esters in food products: 5 February 2009, pages 1-15, XP008168957) (http://www.ilsi.org/Europe/ Speaker%209%20vanDuijn.pdf)
    Summary of the Invention Problems to be Solved by the Invention
  • An object of the present invention is to provide a method for reducing chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester in a glyceride fat or oil.
    • Means for Solving the Problems
  • The present inventors have intensively studied. As a result, they have found that chloropropanols and a glycidol fatty acid ester in a glyceride fat or oil can be reduced by treating a glyceride fat or oil after a bleaching and deodorization step with silica gel and/or basic activated carbon wherein the pH of the basic activated carbon is 9 or higher. The present invention has been completed on the basis of these findings.
  • That is, the present invention provides:
    1. (1) A method for reducing chloropropanols and a glycidol fatty acid ester thereof in a glyceride fat or oil, comprising treating a bleached and deodorized glyceride fat or oil with silica gel and/or basic activated carbon, wherein the pH of the basic activated carbon is 9 or higher,
    2. (2) The method according to (1), wherein the basic activated carbon is hydrophobic activated carbon which has been activated at a high temperature of 500 °C or higher,(3) The method according to (1)or (2), wherein the pH of the basic activated carbon is 10 or higher,
    • (4) The method according to any one of (1) to (3),
    wherein the bleached and deodorized glyceride fat or oil is a palm-base fat or oil, Effect of the Invention
  • According to the method of the present invention, chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester in a glyceride fat or oil can be reduced.
    • Mode for Carrying Out the Invention
  • The present invention will be explained in detail below.
  • The present invention can also be applied to edible refined fats and oils such as soybean oil, rapeseed oil, safflower oil, corn oil, sunflower oil, cottonseed oil, rice oil, olive oil, palm oil, coconut oil, palm kernel oil, sesame oil, beef tallow, lard, and fish oil which are subjected to a refining step such as bleaching and deodorization, and can be preferably applied to a palm-base fat or oil among them.
  • The method of the present invention allows to reduce chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester in a glyceride fat or oil, by treating a glyceride fat or oil after a bleaching and deodorization step with silica gel and/or basic activated carbon. The basic activated carbon is hydrophobic activated carbon which has been activated at a high temperature of 500°C or higher. By using basic activated carbon, chloropropanols and a glycidol fatty acid ester thereof in a glyceride fat or oil can be reduced.
  • In the method of the present invention, the pH of basic activated carbon is 9 or higher, preferably 10 or higher. In addition, when activated carbon having stronger basicity is used, the effect of reducing chloropropanols and a glycidol fatty acid ester thereof in a glyceride fat or oil is higher. In addition, the pH of activated carbon can be measured by the method described in JIS K 1474 "Activated Carbon Test Method".
  • Examples of a method of silica gel treatment and/or active carbon treatment in the present invention include a method of adding 0.1 to 5% by weight of silica gel and/or active carbon to a glyceride fat or oil, and mixing and contacting for a certain period under warming at 50 to 150°C and reduced pressure.
  • The glyceride fat or oil obtained by the method of the present invention has been reduced in the content of chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester. In the present invention, the content of chloropropanols and a glycidol fatty acid ester is measured by the following method by referring to the following reference. (Determination of total 3-chloropropane-1,2-diol (3-MCPD) in edible oils by cleavage of MCPD esters with sodium methoxide. Eur. J. Lipid Sci. Technol. 2008, 110, : 183-186)
  • First, 0.1 g of a fat or oil is dissolved in 1 ml of t-butyl methyl ether, 250 µl of a 20 µg/ml internal standard substance (3-MCPD-d5 ethyl acetate solution) is added, and the mixture is mixed with 1 ml of a NaOCH3 solution (0.5 mol/l NaOCH3 in MeOH) and allowed to stand at room temperature for 10 minutes.
  • Subsequently, 3 ml of hexane, 3 ml of a NaCl solution (NaCl 200 g/water 1 l), and 0.1 ml of glacial acetic acid are added and, after stirring, the upper layer is removed. Further, 3 ml of hexane is added and, after stirring, the upper layer is removed.
  • Then, a phenylboronic acid solution (1 g of phenylboronic acid is dissolved in 4 ml of acetone : water = 19 : 1) is added and, after stirring, the mixture is allowed to stand at 80°C for 20 minutes, and allowed to cool to room temperature. Then, 2 ml of hexane is added, the mixture is stirred, and the upper layer is subjected to GS-GM analysis. In addition, regarding GC-MS, quantitation is carried out by using a molecular ion peak m/z 196 (3-MCPD) and m/z 201 (3-MCPD-d5).
  • The above-mentioned method is adopted as a method of measuring 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester in Germany (Deutsche Gesellschaft fur Fettwissenschaft: DGF). In this method, 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester in a glyceride fat or oil are hydrolyzed, and all of 3-chloropropanediol fatty acid ester and a glycidol fatty acid ester that are present in a glyceride fat or oil are measured as 3-MCPD.
    "With this method, other compounds forming 3-MCPD under the conditions of analysis are also detected. The most important 3-MCPD esters forming compounds is glycidol (oxirane-2-methanol)."
    (Ester-bound 3-chloropropane-1,2-diol (3-MCPD esters) and 3-MCPD forming substances: DGF Standard Methods Section C-Fats/C-III 18(09)).
  • The glyceride fat or oil obtained by the method of the present invention has been reduced in the content of a glycidol fatty acid ester. In the present invention, the content of a glycidol fatty acid ester is measured by the following method.
  • First, 0.15 g of a fat or oil is dissolved in 1.5 ml of acetonitrile containing 1% acetic acid and, after mixing, centrifugation is carried out. Subsequently, 1 ml of the supernatant is fractionated, and the solvent is removed. Subsequently, the fat or oil is dissolved in 1 ml of a mixed solution of acetonitrile : 5 mM ammonium acetate = 4 : 1. Further, after filtration with a 0.45 µ filter, the solution is subjected to LC/MS/MS analysis.
  • In addition, regarding LC/MS/MS, quantitation is carried out in a positive ion mode using a precursor ion m/z 358, a product ion m/z 341 (glycidol stearic acid ester), a precursor ion m/z 356, a product ion m/z 339 (glycidol oleic acid ester), a precursor ion m/z 330, and a product ion m/z 313 (glycidol palmitic acid ester). The detection limit is 0.5 ppm.
  • In the following, examples will be shown and the present invention will be further specifically explained. In the Examples, % means a weight basis.
    • (Comparative Example 1)
  • To a refined palm oil (iodine value: 53) was added 2% by weight of white clay, the mixture was bleached at 110°C and 20 Torr for 10 minutes and, subsequently, a deodorization treatment was carried out at 250°C and 2 Torr for 90 minutes.
  • The content of chloropropanols and a formative substance thereof in the resulting refined palm oil was 6.5 ppm.
    • Example 1
  • To the refined palm oil obtained in Comparative Example 1 was added 3% by weight of silica gel, and the mixture was stirred at 110°C and 20 Torr for 10 minutes to be treated with an adsorbent.
  • The content of chloropropanols and a formative substance thereof in the refined palm oil after the adsorbent treatment was 4.8 ppm.
    • Example 2
  • To the refined palm oil obtained in Comparative Example 1 was added 3% by weight of coconut shell activated carbon (pH 9.7), and the mixture was stirred at 110°C and 20 Torr for 10 minutes to be treated with an activated carbon.
  • The content of chloropropanols and a formative substance thereof in the refined palm oil after the activated carbon treatment was 4.7 ppm.
    • Example 3
  • To the refined palm oil obtained in Comparative Example 1 was added 3% by weight of powdery activated carbon (pH 10.6), and the mixture was stirred at 110°C and 20 Torr for 10 minutes to be treated with an activated carbon.
  • The content of chloropropanols and a formative substance thereof in the refined palm oil after the activated carbon treatment was 4.5 ppm.
    • (Comparative Example 2)
  • To the refined palm oil obtained in Comparative Example 1 was added 3% by weight of phosphoric acid-activated carbon (pH 3.4), and the mixture was stirred at 110°C and 20 Torr for 10 minutes to be treated with an activated carbon.
  • The content of chloropropanols and a formative substance thereof in the refined palm oil after the activated carbon treatment was 7.4 ppm.

Claims (4)

  1. A method for reducing chloropropanols and a glycidol fatty acid ester thereof in a glyceride fat or oil, comprising treating a bleached and deodorized glyceride fat or oil with silica gel and/or basic activated carbon, wherein the pH of the basic activated carbon is 9 or higher.
  2. The method according to claim 1 wherein the basic activated carbon is hydrophobic activated carbon which has been activated at a temperature of 500°C or higher.
  3. The method according to claim 1 or 2, wherein the pH of the basic activated carbon is 10 or higher.
  4. The method according to any one of claims 1 to 3, wherein the bleached and deodorized glyceride fat or oil is a palm-base fat or oil.
EP10820654.1A 2009-09-30 2010-09-30 Method for reducing chloropropanols and formative substance thereof, glycidol fatty acid esters, in glyceride oils Revoked EP2471897B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2009229056 2009-09-30
JP2009229058 2009-09-30
JP2009229057 2009-09-30
JP2009255353 2009-11-06
PCT/JP2010/067110 WO2011040539A1 (en) 2009-09-30 2010-09-30 Method for reducing chloropropanols and formative substance thereof, glycidol fatty acid esters, in glyceride oils

Publications (3)

Publication Number Publication Date
EP2471897A1 EP2471897A1 (en) 2012-07-04
EP2471897A4 EP2471897A4 (en) 2015-03-11
EP2471897B1 true EP2471897B1 (en) 2017-10-11

Family

ID=43826351

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10820654.1A Revoked EP2471897B1 (en) 2009-09-30 2010-09-30 Method for reducing chloropropanols and formative substance thereof, glycidol fatty acid esters, in glyceride oils

Country Status (6)

Country Link
EP (1) EP2471897B1 (en)
JP (1) JP5803671B2 (en)
KR (1) KR101795819B1 (en)
DK (1) DK2471897T3 (en)
MY (1) MY158557A (en)
WO (1) WO2011040539A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2812109C2 (en) * 2019-03-22 2024-01-22 Карджилл, Инкорпорейтед Oil processing

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK2471897T3 (en) 2009-09-30 2018-01-15 Fuji Oil Co Ltd PROCEDURE FOR REDUCING CHLOROPROPANOLS AND CREATING SUBSTANCES, GLYCIDOL FAT ACID ESTERS, IN GLYCERIDE OILS
JP5717351B2 (en) 2010-03-17 2015-05-13 花王株式会社 Method for producing refined fats and oils
DK2611767T3 (en) 2010-09-03 2017-12-11 Stepan Specialty Products Llc ELIMINATION OF ORGANO HALOGENE AND OXIRAN SPECIES IN CARBOXYLIC ACID ESTREAM
HUE054538T2 (en) 2011-02-10 2021-09-28 Cargill Inc Method for reducing the 3-mcpd/glycidyl ester content in oils
JP2011174091A (en) 2011-06-01 2011-09-08 Showa Sangyo Co Ltd Method for producing palm oil having step of removing free chlorine
KR101207413B1 (en) * 2011-06-09 2012-12-04 씨제이제일제당 (주) A method of process for edible oil reduced with 3-chloro-1,2-propanediol forming substances and product prepared thereby
JP6008596B2 (en) * 2011-06-15 2016-10-19 花王株式会社 Method for producing refined fats and oils
MY159241A (en) * 2011-07-29 2016-12-30 Nisshin Oillio Group Ltd Purified glyceride composition and method for producing purified glyceride composition
JP2016169391A (en) * 2011-07-29 2016-09-23 日清オイリオグループ株式会社 Palm-based oil and fat
JP6021382B2 (en) * 2011-07-29 2016-11-09 日清オイリオグループ株式会社 Method for producing glyceride composition
ES2731265T3 (en) 2011-12-23 2019-11-14 Bunge Loders Croklaan B V Method of treating a vegetable oil
JP2013203768A (en) * 2012-03-27 2013-10-07 Nisshin Oillio Group Ltd Method for producing purified glyceride composition
GB201215062D0 (en) * 2012-08-23 2012-10-10 Sericol Ltd A printing ink
CN104711118B (en) * 2013-12-16 2019-02-22 丰益(上海)生物技术研发中心有限公司 A method of reducing trans-fatty acid
JP6441072B2 (en) * 2014-12-26 2018-12-19 ミヨシ油脂株式会社 Method for reducing chloropropanols in edible fats and oils
JP6570832B2 (en) * 2014-12-26 2019-09-04 ミヨシ油脂株式会社 Method for producing edible fat and oil and method for suppressing return odor
MY190874A (en) 2017-03-30 2022-05-13 Sime Darby Plantation Berhad Process for producing a refined vegetable oil
MY193401A (en) 2017-08-04 2022-10-11 Sime Darby Plantation Intellectual Property Sdn Bhd Process for producing a refined palm fruit oil having a reduced 3-mcpd content
MX2020008876A (en) * 2018-03-14 2020-09-25 Nestle Sa Mechanical purification of triacylglyceride oils.
WO2019217223A1 (en) * 2018-05-07 2019-11-14 Arisdyne Systems, Inc. Methods for refined palm oil production with reduced 3-mcpd formation
US11629310B2 (en) * 2018-12-19 2023-04-18 Societe Des Produits Nestle S.A. Purification of triacylglyceride oils by auxiliary washing
CN111330539B (en) * 2018-12-19 2022-08-26 丰益(上海)生物技术研发中心有限公司 Composite solid adsorbent and method for purifying grease
MX2021011483A (en) * 2019-03-22 2021-10-22 Cargill Inc Oil processing.
EP3786266A1 (en) 2019-09-02 2021-03-03 DuPont Nutrition Biosciences ApS A process for reducing glycidyl esters in monoglycerides comprising monounsaturated monoglycerides
EP3786265A1 (en) 2019-09-02 2021-03-03 DuPont Nutrition Biosciences ApS A process for reducing glycidol and glycidyl esters in monoglycerides and/or diglycerides
KR102639280B1 (en) * 2021-07-30 2024-02-20 서울대학교산학협력단 A process for preparing edible oil
CN115820335A (en) * 2022-10-18 2023-03-21 湖南亚美茶油股份有限公司 Processing method of low-condensed glyceride edible oil

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4874629A (en) 1988-05-02 1989-10-17 Chang Stephen S Purification of fish oil
WO2002081719A1 (en) 2001-04-06 2002-10-17 Archer-Daniels-Midland Company Method for producing fats or oils
WO2005010136A2 (en) 2003-07-16 2005-02-03 Archer-Daniels-Midland Company Method for producing fats or oils
EP2471897A1 (en) 2009-09-30 2012-07-04 Fuji Oil Company, Limited Method for reducing chloropropanols and formative substance thereof, glycidol fatty acid esters, in glyceride oils

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2975060A (en) * 1955-02-19 1961-03-14 Lever Brothers Ltd Cocoa butter substitutes and products containing them
JPS52117305A (en) * 1976-03-26 1977-10-01 Kanegafuchi Chem Ind Co Ltd Solvent fractionation of fat and oil
JP4457553B2 (en) 2001-12-10 2010-04-28 不二製油株式会社 Confectionery fats and oils, production method thereof, and confectionery fats and oils products using the same
JP5101206B2 (en) 2007-08-08 2012-12-19 花王株式会社 Process for producing fats and oils with high diacylglycerol content
WO2009075278A1 (en) 2007-12-12 2009-06-18 Fuji Oil Company, Limited Refined palm-based fat or oil and method of producing the same
DE102008060059A1 (en) * 2008-12-02 2010-06-10 Süd-Chemie AG Method for reducing the 3-MCPD content in refined vegetable oils
SG177423A1 (en) 2009-06-30 2012-02-28 Sime Darby Malaysia Berhad Process for removing unwanted propanol components from unused triglyceride oil
JP5700503B2 (en) * 2009-09-07 2015-04-15 日清オイリオグループ株式会社 Glyceride composition and method for producing the glyceride composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4874629A (en) 1988-05-02 1989-10-17 Chang Stephen S Purification of fish oil
CA1335110C (en) 1988-05-02 1995-04-04 Stephen S. Chang Purification of fish oil
WO2002081719A1 (en) 2001-04-06 2002-10-17 Archer-Daniels-Midland Company Method for producing fats or oils
WO2005010136A2 (en) 2003-07-16 2005-02-03 Archer-Daniels-Midland Company Method for producing fats or oils
EP2471897A1 (en) 2009-09-30 2012-07-04 Fuji Oil Company, Limited Method for reducing chloropropanols and formative substance thereof, glycidol fatty acid esters, in glyceride oils

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
GARY R.: "Bleaching and Purifying Fats and Oils. 2nd ed.", 2009, AOCS PRESS, pages: 79 - 95, XP055501308
GERRIT VAN DUIJN: "Potential ways of reduction of 3-MCPD esters in vegetable oils", ILSI CONFERENCE, 5 February 2009 (2009-02-05), XP008168957
J. VELISEK: "3-Chloropropane-1,2-diol in Models Simulating Processed Foods: Precursors and Agents Causing its Decomposition", CZECH J. FOOD SCI., vol. 21, no. 5, 2003, pages 153 - 161, XP002724387
K. FRANCKE: "Influence of chemical refining process and oil type on bound 3-chloro-1,2-propanediol contents in palm oil and rapeseed oil", LWT FOOD SCIENCE AND TECHNOLOGY, vol. 42, no. 10, December 2009 (2009-12-01), pages 1751 - 1754, XP026502436

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2812109C2 (en) * 2019-03-22 2024-01-22 Карджилл, Инкорпорейтед Oil processing

Also Published As

Publication number Publication date
DK2471897T3 (en) 2018-01-15
WO2011040539A1 (en) 2011-04-07
KR101795819B1 (en) 2017-11-09
JPWO2011040539A1 (en) 2013-02-28
KR20120091025A (en) 2012-08-17
MY158557A (en) 2016-10-14
JP5803671B2 (en) 2015-11-04
EP2471897A1 (en) 2012-07-04
EP2471897A4 (en) 2015-03-11

Similar Documents

Publication Publication Date Title
EP2471897B1 (en) Method for reducing chloropropanols and formative substance thereof, glycidol fatty acid esters, in glyceride oils
WO2010126136A1 (en) Method for inhibiting production of chloropropanols and chloropropanol-forming substances in glyceride oils and fats
US9051260B2 (en) Elimination of organohalo and oxirane species in carboxylic acid ester streams
US9217120B2 (en) Method of treating a vegetable oil
EP2053118B1 (en) Emulsification-free degumming of oil
EP2548941B1 (en) Production process for refined fat or oil
EP2738243B1 (en) Purified glyceride composition and method for producing purified glyceride composition
JP2011144343A (en) Manufacturing method of refined oil and fat
JP5399544B1 (en) Method for producing refined fats and oils
KR20110085143A (en) A process for preparing low 3-mcpd-fs edible oil
JPWO2011055732A1 (en) Method for reducing chloropropanols and substances formed in glyceride oils and fats
KR20110085142A (en) A process for preparing low 3- mcpd-fs edible oil
WO2011138957A1 (en) Method for purification of edible oil or fat
WO2015146248A1 (en) Production method for purified palm oil and fat
JP6639149B2 (en) Method for producing refined fats and oils
JP3390556B2 (en) Stabilized tocopherol-containing fat and oil composition
JPWO2011081119A1 (en) Method for inhibiting the formation of chloropropanols and their forming substances in glyceride oils and fats
KR20120135161A (en) A process for preparing low 3-mcpd-fs edible oil
JP6392517B2 (en) Oil composition
WO2015115584A1 (en) Fat or oil composition
JP2015067692A (en) Method for producing refined fat
CN114845556A (en) Edible oil and fat with reduced content of glycidol and fatty acid ester of glycidol, and its preparation method
JP2021195471A (en) Method for reducing 3-mcpd content in fats and oils

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120330

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
TPAC Observations filed by third parties

Free format text: ORIGINAL CODE: EPIDOSNTIPA

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: FUJI OIL COMPANY, LIMITED

A4 Supplementary search report drawn up and despatched

Effective date: 20150205

RIC1 Information provided on ipc code assigned before grant

Ipc: C11B 3/10 20060101AFI20150130BHEP

Ipc: A23D 9/02 20060101ALI20150130BHEP

17Q First examination report despatched

Effective date: 20160624

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C11B 3/10 20060101AFI20170328BHEP

Ipc: A23D 9/02 20060101ALI20170328BHEP

Ipc: C11B 3/14 20060101ALI20170328BHEP

INTG Intention to grant announced

Effective date: 20170421

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KURIYAMA, MASAMITSU

Inventor name: KUROSAWA, YOKO

Inventor name: INOUE, TOMOMI

Inventor name: MORITA, AKIRA

Inventor name: OMORI, HITOMI

Inventor name: YOKOMIZO, FUTOSHI

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 936017

Country of ref document: AT

Kind code of ref document: T

Effective date: 20171115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602010045953

Country of ref document: DE

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

Effective date: 20180111

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 936017

Country of ref document: AT

Kind code of ref document: T

Effective date: 20171011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180111

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180112

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180211

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180111

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602010045953

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

26 Opposition filed

Opponent name: CARGILL, INCORPORATED

Effective date: 20180704

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20180930

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180930

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180930

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180930

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20190820

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180930

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20190918

Year of fee payment: 10

Ref country code: DK

Payment date: 20190920

Year of fee payment: 10

Ref country code: FR

Payment date: 20190820

Year of fee payment: 10

REG Reference to a national code

Ref country code: DE

Ref legal event code: R064

Ref document number: 602010045953

Country of ref document: DE

Ref country code: DE

Ref legal event code: R103

Ref document number: 602010045953

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180930

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20100930

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171011

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171011

REG Reference to a national code

Ref country code: FI

Ref legal event code: MGE

27W Patent revoked

Effective date: 20200121